Carbonylative Coupling of Alkyl Zinc Reagents with Benzyl Bromides Catalyzed by a Nickel/NN2Pincer Ligand Complex

An efficient catalytic protocol for the three‐component assembly of benzyl bromides, carbon monoxide, and alkyl zinc reagents to give benzyl alkyl ketones is described, and represents the first nickel‐catalyzed carbonylative coupling of two sp3‐carbon fragments. The method, which relies on the application of nickel complexed with an NN2‐type pincer ligand and a controlled release of CO gas from a solid precursor, works well with a range of benzylic bromides. Mechanistic studies suggest the intermediacy of carbon‐centered radicals.